EP1883986B1 - Matrice d'electrolyte pour piles a combustible a carbonate fondu presentant une taille de pores amelioree et procede permettant de produire celle-ci - Google Patents

Matrice d'electrolyte pour piles a combustible a carbonate fondu presentant une taille de pores amelioree et procede permettant de produire celle-ci Download PDF

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EP1883986B1
EP1883986B1 EP06759482A EP06759482A EP1883986B1 EP 1883986 B1 EP1883986 B1 EP 1883986B1 EP 06759482 A EP06759482 A EP 06759482A EP 06759482 A EP06759482 A EP 06759482A EP 1883986 B1 EP1883986 B1 EP 1883986B1
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Prior art keywords
matrix
electrolyte
accordance
making
milling
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German (de)
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EP1883986A4 (fr
EP1883986A2 (fr
Inventor
Gengfu Xu
Chao-Yi Yuh
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Fuelcell Energy Inc
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Fuelcell Energy Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/14—Fuel cells with fused electrolytes
    • H01M8/141—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers
    • H01M8/142—Fuel cells with fused electrolytes the anode and the cathode being gas-permeable electrodes or electrode layers with matrix-supported or semi-solid matrix-reinforced electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/14—Fuel cells with fused electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H01M8/0295—Matrices for immobilising electrolyte melts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/14—Fuel cells with fused electrolytes
    • H01M8/144—Fuel cells with fused electrolytes characterised by the electrolyte material
    • H01M8/145—Fuel cells with fused electrolytes characterised by the electrolyte material comprising carbonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to fuel cells and, in particular, to an electrolyte matrix for use in molten carbonate fuel cells.
  • a fuel cell is a device which directly converts chemical energy stored in hydrocarbon fuel into electrical energy by means of an electrochemical reaction.
  • a fuel cell comprises an anode and a cathode separated by an electrolyte, which serves to conduct electrically charged ions.
  • electrolyte which serves to conduct electrically charged ions.
  • a number of individual fuel cells are stacked in series with an electrically conductive separator plate between each cell.
  • MCFCs Molten carbonate fuel cells
  • the anode and the cathode of MCFCs are isolated from one another by a porous electrolyte matrix which is saturated with carbonate electrolyte.
  • the matrix typically comprises a porous, unsintered y-LiAlO 2 ceramic powder bed impregnated with molten alkali carbonate electrolyte and provides ionic conduction and gas sealing.
  • the matrix experiences both mechanical and thermal stresses which contribute to cracking or defects in the matrix.
  • the electrolyte matrix In order to provide effective gas sealing, the electrolyte matrix must have sufficient strength, mechanical integrity and materials endurance to withstand these stresses, particularly during thermal cycles of the MCFC.
  • the matrix must be able to accommodate volume changes associated with carbonate melting and solidification during MCFC thermal cycling, to provide resistance to pressure differences across the matrix and to wet seal holding pressure over long periods of time, and must have slow or no pore growth over MCFC lifetime.
  • the matrix must have sufficient porosity and sub-micron pore distribution to ensure strong capillary forces so as to effectively retain electrolyte within its pores to prevent flooding of the electrodes and the drying out of the matrix.
  • U.S. Patent No. 4,322,482 discloses use of "crack attenuator" particles having a larger size in the matrix to reduce through-cracking of the matrix.
  • Another method of manufacturing an electrolyte matrix having increased strength and improved uniformity is disclosed in U.S. Patent No. 5,869,203 , assigned to the same assignee herein.
  • the '203 patent discloses a method of fabricating the electrolyte matrix comprising ceramic support material and an additive material employing a high-energy intensive milling technique of the support and additive materials to produce highly active particles of smaller size.
  • the high-energy milling technique of the '203 patent is carried out by adding the additive material to a slurry of the support material and milling the slurry mixture such that the particle size of the additive is less than 0.5 ⁇ m.
  • the matrix is then formed from the slurry mixture by a tape casting technique.
  • the high-energy milling technique of the '203 patent has been effective in increasing the strength and uniformity of the electrolyte matrix.
  • particle packing and pore structure of the matrix fabricated using the conventional methods, including the method disclosed in the '203 patent are significantly affected by the environmental conditions, and particularly by humidity, and the process conditions during the tape casting process as well as by variations in the raw matrix materials.
  • increased humidity leads to undesired non-uniform pore structure of the matrix which, in turn, has a negative effect on the strength of the matrix and its ability to retain electrolyte in its pores.
  • This sensitivity of the tape casting process to the environmental and process conditions and to the raw materials variations often results in a variety of surface defects, cracking and non-uniform structure of the electrolyte matrix.
  • a method of making a matrix element for carrying a carbonate electrolyte comprising providing a carbonate electrolyte material, pre-milling the carbonate electrolyte material to form a pre-milled carbonate electrolyte having a particle size of less than 0.3 microns, providing a support material, mixing the pre-milled carbonate electrolyte with the support material using a milling technique to form a mixture, and forming the mixture into the matrix element.
  • the method may further comprise providing one or more additive components to the mixture of pre-milled carbonate electrolyte and support material, wherein the additive components include at least one of a binder and a plasticizer.
  • Acryloid binder and Santicizer® plasticizer may be used as the additive components.
  • the forming of the matrix element is carried out by casting the mixture and then drying the casted mixture to form a tape element, and may further include heating the tape element to remove the dispersant from the tape element.
  • a fuel cell comprising an electrolyte matrix prepared according to this method is also disclosed.
  • the matrix 2 comprises a support material, one or more additive components and carbonate electrolyte.
  • the support material comprises a porous ceramic material having a sub-micron particle size.
  • LiAlO 2 including ⁇ -LiAlO 2 , ⁇ -LiAlO 2 and ⁇ -LiAlO 2 , are used as the support material.
  • the additive components may include binder, plasticizer and other suitable materials.
  • the electrolyte is disposed in the pores of the support material and comprises an alkali carbonate, such as Li 2 CO 3 , K 2 CO 3 or Na 2 CO 3 . It is understood that other materials may be suitable for use in the electrolyte matrix 2 of the fuel cell.
  • FIG. 2 shows a flow diagram of a method for fabricating the matrix 2 of FIG. 1 in accord with the principles of the present invention.
  • the carbonate electrolyte is pre-milled so that the mean particle size of the resulting pre-milled electrolyte is equal to or is smaller than the mean particle size of the ceramic support material.
  • the total surface area of the carbonate electrolyte particles will be equal to or greater than the total surface area of the support material particles.
  • the desired mean particle size of the carbonate electrolyte should be less than 0.3 microns.
  • the pre-milling of the carbonate electrolyte may be accomplished in the presence of a dispersant.
  • the dispersant is used to disperse the electrolyte so as to prevent re-agglomeration of electrolyte particles.
  • Dispersants such as fish oil and one or more of Hypermer KD-series polymeric dispersants are suitable for dispersing electrolyte during the pre-milling process.
  • the amount of dispersant used may be varied based on the targeted surface area of the pre-milled electrolyte.
  • the pre-milled electrolyte is mixed with the support material, which will form the body of the prepared electrolyte matrix 2 shown in FIG. 1 .
  • the support material typically comprises a ceramic material such as, for example, LiAlO 2 .
  • a third step S103 the mixture prepared in the second step S102 is milled for a predetermined period of time to break down any agglomerates present in the mixture and to form a slurry having the support material particles and the electrolyte particles uniformly dispersed throughout the slurry.
  • the milling of the mixture can be accomplished using any conventional milling process, such as attrition milling, ball milling or fluid energy grinding.
  • organic additives may be added to the slurry prepared in step S103 to prevent cracking of the matrix 2 prepared using this method.
  • the cracking of the matrix may occur when the matrix is used in a fuel cell during operation as a result of the increased overall surface area of the matrix.
  • These additives may include a binder and a plasticizer.
  • acryloid binder and Santicizer® 160 plasticizer are suitable for use as the organic components to be added to the slurry.
  • the amount of organic additives added to the slurry may comprise approximately 10 to 30 % by weight of all solid components, i.e. electrolyte, support material and additives, of the slurry.
  • the slurry mixed with organic additives in the fourth step S104 is formed into one or more electrolyte matrix elements in a fifth step S105 of the matrix fabrication method.
  • the electrolyte matrix elements may be formed by any suitable conventional technique. Tape casting is a preferred technique for forming the matrix element in which the slurry is tape cast using a doctor blade and then dried. The dry tape cast slurry results in a flat and flexible green tape having nearly theoretical as-cast green density and nearly 0% green porosity. The green tape then undergoes a burnout procedure during which the tape is heated to a predetermined temperature for a predetermined period of time to remove the dispersant by combustion and to produce a completed electrolyte matrix element. As can be appreciated, a plurality of green tapes may be prepared from the slurry to form multiple completed matrix elements.
  • the completed matrix element comprises the ceramic matrix 2 formed from the support material with the carbonate electrolyte particles dispersed in the matrix.
  • the carbonate electrolyte particles define the pore sizes in the matrix.
  • LiAlO 2 is used as the support material in the matrix and Li 2 CO 3 is the electrolyte material.
  • the method shown in FIG. 2 and described above is used to fabricate matrix elements filled with electrolyte in accord with the invention.
  • Li 2 CO 3 is pre-milled to a mean particle size of less than 0.3 microns, and preferably 0.1 to 0.2 microns. Since a typical surface area of LiAlO 2 particles is 10 m 2 /g, the desired surface area of pre-milled Li 2 CO 3 particles is about 10 m 2 /g.
  • the Li 2 CO 3 is pre-milled in the presence of a fish oil dispersant to prevent re-agglomeration of the Li 2 CO 3 particles after the pre-milling step.
  • the amount of fish oil used in this step is equal to approximately 1 to 5% of the weight of Li 2 CO 3 .
  • an attrition milling technique using YTZ® grinding media having 2 to 6 mm ball size is employed to pre-mill Li 2 CO 3 to the particle size between 0.1 and 0.2 microns.
  • the grinding media loading is between 60 and 80%, and preferably about 70%, and the grinding speed is between 2,000 and 3,000 rpm.
  • step S 102 the pre-milled Li 2 CO 3 is mixed with the support material LiAlO 2 and in the third step S103, the resulting mixture is milled for approximately 2 hours to form a slurry.
  • step S103 the attrition milling technique is employed. During this step, any agglomerates present in the mixture are broken down and the Li 2 CO 3 and LiAlO 2 particles are uniformly dispersed throughout the slurry.
  • additives including a binder and a plasticizer
  • acryloid binder and Santicizer® 160 plasticizer are used as the additives.
  • the amount of these additives added to the slurry in this example is approximately 21 % by weight of all solid components, i.e. Li 2 CO 3 , LiAlO 2 and additives, of the slurry.
  • the mixture of the slurry and the additives is then formed into electrolyte matrix elements using the tape casting technique.
  • the slurry is tape cast using a doctor blade and dried at about 60° Celsius for 0.5 hours, to form a plurality of green tapes. These tapes are then heated to a temperature of about 400° Celsius for approximately 2 hours to remove the fish oil dispersant by combustion and to produce completed electrolyte matrix elements.
  • the electrolyte matrix elements fabricated using the above method have improved particle packing, unique narrow pore size distribution and significantly improved mechanical strength.
  • the pore structure of these electrolyte matrix elements is more refined, having smaller mean pore size and narrower pore size distribution as compared with conventional electrolyte matrix.
  • the smaller mean pore size and narrower pore size distribution contribute to the improved strength and endurance of the matrix during MCFC thermal cycling and to greater electrolyte retention by the matrix.
  • FIG. 3 shows a graph of pore size distribution data for electrolyte matrix tapes fabricated using the method of FIG. 2 and for conventional electrolyte matrix tapes prepared using the method described in the ⁇ 203 patent.
  • the matrix tapes prepared using either of these methods were formed from the same components.
  • LiAlO 2 was used as the support material for the matrix tapes and Li 2 CO 3 was used as the electrolyte.
  • the X-axis represents the pore size of the matrix in microns
  • the Y-axis represents a log differential for the cumulative pore volume in mL/g.
  • the conventional matrix tapes had a broad dual-peak pore size distribution with pores ranging between 0.04 and 0.6 microns in size.
  • the conventional tapes had a frequent occurrence of larger pores having a pore size of about 0.5 microns as well as a large number of smaller pores having a pore size of about 0.14 microns.
  • the matrix tapes fabricated using the method of FIG. 2 employing pre-milling of Li 2 CO 3 had a significantly narrower single-peak pore size distribution with pores ranging between 0.04 microns and 0.3 microns in size.
  • the peak number of pores in these matrix tapes had a pore size of about 0.14 microns.
  • FIG. 4 shows a bar graph of the bending strengths of matrix tapes formed from different types of LiAlO 2 powder which were prepared with or without the pre-milling of Li 2 CO 3 .
  • the bending strengths of the conventional electrolyte matrix samples formed with ⁇ -LiAlO 2 having 94% purity, 0.15 micron primary particle size and 10 m 2 /g surface area (Powder A) and ⁇ -LiAlO 2 having 96% purity, 0.11 micron primary particle size and 11 m 2 /g surface area (Powder B) were approximately 380 psi and 400 psi, respectively.
  • the bending strength of an electrolyte matrix sample prepared using the method of FIG. 2 with Powder A was about 625 psi
  • the bending strength of a sample prepared using the method of FIG. 2 with Powder B was about 680 psi
  • FIG. 5 shows a graph of pore size distribution data for the electrolyte matrix samples tested.
  • the X-axis represents the pore size in microns, while the Y-axis represents a relative frequency of occurrence.
  • the electrolyte matrix samples prepared with Powder A had a pore size distribution between 0.08 and 0.5 microns, with the most frequently occurring pores being in the pore size range between 0.1 and 0.3 microns.
  • the electrolyte matrix samples prepared with Powder B or Powder C had a pore size distribution between 0.05 and 0.2 microns.
  • the majority of the pores in the sample prepared with Powder B had a pore size of approximately 0.1 microns.
  • the most frequently occurring pore sizes were between 0.07 and 0.2.
  • the pre-milling of Li 2 CO 3 during the fabrication of the samples eliminated the dual-peak pore size distribution, regardless of the purity of the LiAlO 2 support material and resulted in a narrower, and thus more uniform, pore size distribution in each of the samples.
  • the effect of environmental humidity during the tape casting step S 104 on the pore size distribution in the electrolyte matrix samples prepared using the method of FIG. 2 was also tested.
  • the electrolyte matrix samples were formed with LiAlO 2 support materials at 27% and 57% humidity levels.
  • FIG. 6 shows a graph of pore size distribution data of the electrolyte matrix samples 601-604 formed at these humidity levels.
  • the samples 601, 602 and 603 were each formed with LiAlO 2 powder having 94% purity (Powder A) using the tape casting technique at 27% relative humidity, while sample 604 was formed with Powder A by tape casting at 57% relative humidity.
  • the pore size distribution of each of the samples 601-604 was between 0.03 and 0.3 with the peak number of pores having a size of approximately 0.19 microns.
  • the humidity during the tape casting process was increased from 27% to 57%, the pore size distribution of the completed matrix elements remained about the same as the pore size distribution of the samples formed at 27% humidity. Accordingly, it can be seen that the environmental humidity during the tape casting process has little or no effect on the pore size distribution, and thus on the mechanical integrity and electrolyte retention characteristics, of the completed electrolyte matrix samples fabricated using the method of FIG. 2 .
  • the lifetime of the MCFC is affected by a variety of factors including loss of electrolyte, the drying out of the matrix, the strength of the matrix and its gas sealing capacity.
  • pores having a size greater than 0.3 microns in conventional electrolyte matrices contribute to a loss of approximately 30% of the electrolyte stored in the matrix.
  • smaller pores and more uniform porosity of the matrix fabricated in accordance with the present invention significantly reduce the loss of electrolyte from the matrix, preventing the drying out of the matrix and a possible cross-over of the fuel and oxidant gases.
  • the improved strength and characteristics of the electrolyte matrix prepared as shown in FIG. 2 significantly reduce the risk of cracking of the matrix. Therefore, the improvements in the electrolyte matrix fabricated in accord with the invention increase the operating life of MCFCs.
  • FIG. 7 shows a graph of projected MCFC lifetime for single-cell MCFCs and MCFC stacks using conventional electrolyte matrices and for single-cell MCFCs and stacks using electrolyte matrices prepared using the method of FIG. 2 .
  • the X-axis represents the lifetime of the fuel cell in hours, while the Y-axis represents the actual electrolyte fill level of the fuel cells.
  • the lifetimes of MCFCs and stacks were determined based on the fill level of the Li 2 CO 3 electrolyte in the cells, with a minimum electrolyte fill level required for MCFC operation being about 75%.
  • the minimum electrolyte fill level was reached after about 3,500 hours of operation, this operating time representing a projected lifetime of conventional single-cell MCFCs.
  • the projected lifetime of single-cell MCFCs 702 which employed electrolyte matrices fabricated using the method of FIG. 2 was increased to about 6,900 hours due to the improved electrolyte retention of these cells.
  • a similar increase in a projected lifetime can be seen for MCFC stacks.
  • the lifetime of conventional MCFC stacks 703 is approximately 14,000 hours, while the lifetime of MCFC stacks 704 with the matrices prepared using pre-milling of the electrolyte is about 28,000 hours.
  • the improved electrolyte retention by electrolyte matrices fabricated in accord with the invention results in nearly doubling the operating life of the MCFC cells and stacks.
  • the improvements in the strength of the matrix and the reduced risk of matrix cracking also contribute to extending the lifetime of MCFCs.

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Abstract

L'invention concerne un procédé permettant de produire une matrice supportant un électrolyte de carbonate, consistant à préparer un matériau d'électrolyte à base de carbonate, à pré-concasser l'électrolyte de carbonate pour former un électrolyte de carbonate présentant une taille de particules inférieure à 0,3 micromètres, à préparer un matériau de support, à mélanger l'électrolyte de carbonate pré-concassé au matériau de support par un procédé de broyage, de manière de former un mélange, et à façonner ce mélange pour former la matrice

Claims (20)

  1. Procédé de fabrication d'un élément matriciel destiné à porter un électrolyte de carbonate comprenant :
    la fourniture d'un matériau d'électrolyte de carbonate ;
    le prébroyage dudit matériau d'électrolyte de carbonate afin de former un électrolyte de carbonate prébroyé d'une grosseur de particules de moins de 0,3 microns ;
    la fourniture d'un matériau de support ;
    le mélange dudit électrolyte de carbonate prébroyé avec ledit matériau de support au moyen d'une technique de broyage afin de former un mélange ; et
    la formation dudit mélange en ledit élément matriciel.
  2. Procédé de fabrication d'un élément matriciel selon la revendication 1, dans lequel ledit matériau de support est LiAlO2.
  3. Procédé de fabrication d'un élément matriciel selon la revendication 1, dans lequel ledit matériau d'électrolyte de carbonate est l'un ou plusieurs de Li2CO3, K2CO3 et Na2CO3.
  4. Procédé de fabrication d'un élément matriciel selon la revendication 1, dans lequel la fourniture dudit électrolyte de carbonate comporte la dispersion dudit électrolyte dans une quantité prédéterminée de dispersant et ledit prébroyage est effectué avec ledit électrolyte de carbonate dispersé dans ledit dispersant.
  5. Procédé de fabrication d'un élément matriciel selon la revendication 4, dans lequel ladite quantité prédéterminée dudit dispersant est égale à 1 à 5 % d'électrolyte de carbonate en poids.
  6. Procédé de fabrication d'un élément matriciel selon la revendication 5, dans lequel ledit dispersant est l'un d'huile de poisson et de dispersant polymère Hypermer série KD.
  7. Procédé de fabrication d'un élément matriciel selon la revendication 4, comprenant en outre la fourniture d'au moins un composant additif audit mélange dudit électrolyte de carbonate prébroyé et dudit matériau de support.
  8. Procédé de fabrication d'un élément matriciel selon la revendication 7, dans lequel lesdits composants additifs comportent au moins l'un d'un liant et d'un plastifiant.
  9. Procédé de fabrication d'un élément matriciel selon la revendication 8, dans lequel ledit liant comprend un liant d'acryloïde et ledit plastifiant comprend un plastifiant Santicizer® 160.
  10. Procédé de fabrication d'un élément matriciel selon la revendication 1, dans lequel ladite formation dudit élément matriciel comporte la coulée dudit mélange puis le séchage dudit mélange coulé afin de former un élément de ruban.
  11. Procédé de fabrication d'un élément matriciel selon la revendication 10, dans lequel ladite formation comporte en outre le chauffage dudit élément de ruban afin d'éliminer ledit dispersant dudit élément de ruban
  12. Procédé de fabrication d'un élément matriciel selon la revendication 1, dans lequel ledit prébroyage dudit électrolyte de carbonate comporte le prébroyage dudit électrolyte à une grosseur de particules de 0,1 à 0,2 microns.
  13. Procédé de fabrication d'un élément matriciel selon la revendication 12, dans lequel une superficie dudit matériau de support est de 10 m2/g et une superficie dudit électrolyte de carbonate prébroyé est de 10 m2 /g.
  14. Procédé de fabrication d'un élément matriciel selon la revendication 12, dans lequel ledit prébroyage dudit électrolyte de carbonate comprend le broyage par attrition.
  15. Procédé de fabrication d'un élément matriciel selon la revendication 14, dans lequel ledit broyage par attrition est effectué en utilisant des corps de broyage YTZ® ayant une grosseur de billes entre 2 et 6 mm à une charge de corps de broyage entre 60 et 80% et une vitesse de broyage entre 2000 et 3000 tr/min.
  16. Procédé de fabrication d'un élément matriciel selon la revendication 15, dans lequel ladite charge du corps de broyage est 70%.
  17. Procédé de fabrication d'un élément matriciel selon la revendication 15, dans lequel :
    la fourniture dudit électrolyte de carbonate comporte la dispersion dudit électrolyte dans une quantité prédéterminée de dispersant et ledit prébroyage est effectué avec ledit électrolyte de carbonate dispersé dans ledit dispersant ; ladite formation dudit élément matriciel comporte la coulée dudit mélange, puis le séchage dudit mélange coulé afin de former un élément de ruban comportant le chauffage dudit élément de ruban afin d'éliminer ledit dispersant dudit élément de ruban ; et dans lequel ledit électrolyte de carbonate est Li2CO3 et ledit dispersant est de l'huile de poisson, et dans lequel ledit chauffage dudit élément matriciel comporte le chauffage dudit élément à 400°Celsius pendant 2 heures.
  18. Pile à combustible comprenant:
    une section d'anode ;
    une section de cathode ;
    une matrice d'électrolyte disposé entre ladite section d'anode et ladite section de cathode, ladite matrice d'électrolyte comprenant au moins un matériau de support ; et
    un électrolyte de carbonate disposé à l'intérieur de ladite matrice ;
    dans laquelle la matrice a une répartition volumétrique des pores à pic unique étroit avec des pores mesurant entre 0,04 microns et 0,3 microns ; et
    dans laquelle ladite matrice est formée par un procédé selon l'une quelconque des revendications 1 à 17.
  19. Pile à combustible selon la revendication 18, dépendant de la revendication 9, dans laquelle ledit électrolyte de carbonate est Li2CO3 et ledit dispersant est de l'huile de poisson, et dans laquelle ledit prébroyage dudit Li2CO3 est effectué en utilisant l'une des opérations de broyage par attrition, broyage à billes et broyage par énergie fluidique et dans laquelle une quantité dudit dispersant est égale à 1 à 5% de poids d'électrolyte de carbonate.
  20. Pile à combustible selon la revendication 19, dans lequel ledit prébroyage est un broyage par attrition effectué en utilisant des corps de broyage YTZ® ayant une grosseur de billes entre 2 et 6 mm à une charge de corps de broyage entre 60 et 80% et une vitesse de broyage entre 2000 et 3000 tr/min et dans laquelle ledit chauffage dudit élément de ruban comporte le chauffage dudit élément à 400° Celsius pendant 2 heures.
EP06759482A 2005-05-13 2006-05-10 Matrice d'electrolyte pour piles a combustible a carbonate fondu presentant une taille de pores amelioree et procede permettant de produire celle-ci Expired - Fee Related EP1883986B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/128,909 US20060257721A1 (en) 2005-05-13 2005-05-13 Electrolyte matrix for molten carbonate fuel cells with improved pore size and method of manufacturing same
PCT/US2006/018066 WO2006124449A2 (fr) 2005-05-13 2006-05-10 Matrice d'electrolyte pour piles a combustible a carbonate fondu presentant une taille de pores amelioree et procede permettant de produire celle-ci

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KR101146944B1 (ko) 2010-04-14 2012-05-22 두산중공업 주식회사 대면적 전해질 함침형 공기극 제조방법
US9225030B1 (en) * 2011-06-20 2015-12-29 University Of South Carolina Mixed proton and carbonate ion conductor
US20150214564A1 (en) 2014-01-27 2015-07-30 Fuelcell Energy, Inc. Fuel cell matrix composition and method of manufacturing same
KR101795894B1 (ko) * 2015-12-24 2017-12-01 주식회사 포스코 산화물계 전해질 이동 차단층이 형성된 용융탄산염 연료전지용 가스켓
CN110911717B (zh) * 2019-12-03 2021-03-23 中国华能集团清洁能源技术研究院有限公司 一种熔融碳酸盐燃料电池堆电解质补充方法
CN112928318A (zh) * 2021-03-18 2021-06-08 华能国际电力股份有限公司 一种无粘结剂的熔融碳酸盐燃料电池电解质膜及其制备方法

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KR101320195B1 (ko) 2013-10-30
KR20080011694A (ko) 2008-02-05
CN101443942A (zh) 2009-05-27
JP2008541385A (ja) 2008-11-20
US20060257721A1 (en) 2006-11-16
EP1883986A4 (fr) 2009-06-24
WO2006124449A2 (fr) 2006-11-23
WO2006124449A3 (fr) 2008-08-28
EP1883986A2 (fr) 2008-02-06

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